View PDF Version
 
DOI: 10.1039/A800890F (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1998, 1581-1586

Synthesis and characterisation of derivatives of monocyclopentadienylbis(arene-1,2-dithiolato)titanium(IV); crystal structures of M[Ti(η5-C5Me5)(1,2-S2C6H4)2] [M = Tl or N(PPh3)2]

(Note: The full text of this document is currently only available in the PDF Version )

Malcolm A. Spence, Georgina M. Rosair and W. Edward Lindsell

Abstract

Thallium(I) derivatives of monocyclopentadienylbis(arene-1,2-dithiolato)titanium, Tl[Ti(η5-C5HnMe5 – n)(S2C6H3R)2 (1–6; n = 0, 4 or 5; R = H or Me), have been synthesised and isolated in yields of 31–65% from reactions of the corresponding trichloromonocyclopentadienyltitanium reagents, Ti(η5-C5HnMe5 – n)Cl3 and thallium salts of the benzene-1,2-dithiol or toluene-3,4-dithiol in tetrahydrofuran. Reaction between Tl[Ti(η5-C5Me5)(1,2-S2C6H4)2] and bis(triphenylphosphine)iminium chloride, [N(PPh3)2]Cl, has also afforded the derivative [N(PPh3)2][Ti(η5-C5Me5)(1,2-S2C6H4)2] 7. Products have been characterised by elemental analysis, NMR, IR and mass spectroscopy, and by X-ray diffraction. The structure of 7, in the crystalline state as a tris(dichloromethane) solvate, comprises an ionic lattice containing discrete [Ti(η5-C5Me5)(1,2-S2C6H4)2]– anions of four-legged piano stool geometry with two chelating benzene-1,2-dithiolate ligands folded along the S[hair space][hair space]· · ·[hair space][hair space]S axis in exo and endo conformations, respectively, relative to the cyclopentadienyl ring. The crystal structure of Tl[Ti(η5-C5Me5)(S2C6H4)2] 1 contains two forms of the anion [Ti(η5-C5Me5)(S2C6H4)2]– in endo/endo and endo/exo conformations, respectively, which are unsymmetrically co-ordinated to the TlI cations. A TlI ion is connected by two Tl–S bonds to endo dithiolate ligands of each anion and there is also one Tl–S interaction between pairs of endo/endo and endo/exo forms. Additional weaker Tl[hair space][hair space]· · ·[hair space][hair space]S interactions to the TlI ions generate a linked chain of dimeric units. In solution, NMR spectra suggest a more symmetrical structure for all derivatives but shifts in resonances support the retention of co-ordinate links between the cyclopentadienylbis(arene-1,2-dithiolato)titanium anion and TlI.

References

  1. J. L. Davidson, B. Holtz, W. E. Lindsell and N. J. Simpson, J. Chem. Soc., Dalton Trans., 1996, 4011 RSC and refs. therein.
  2. W. A. W. Abu Bakar, J. L. Davidson, W. E. Lindsell, K. J. McCullough and K. W. Muir, J. Chem. Soc., Dalton Trans., 1989, 991 RSC; W. A. E. Abu Bakar, J. L. Davidson, W. E. Lindsell and K. J. McCullough, J. Chem. Soc., Dalton Trans., 1990, 61 RSC.
  3. See, for example, D. W. Stephan and T. T. Nadasdi, Coord. Chem. Rev., 1996, 147, 147 Search PubMed.
  4. H. Köpf and B. Block, Z. Naturforsch., Teil B, 1968, 23, 1534 Search PubMed.
  5. T. Klapötke, R. Laskowski and H. Köpf, Z. Naturforsch., Teil B, 1987, 42, 777; T. Klapötke, H. Köpf and P. Gowik, J. Chem. Soc., Dalton Trans., 1988, 1529 RSC.
  6. T. T. Nadasdi, Y. Huang and D. W. Stephan, Inorg. Chem., 1993, 32, 347 CrossRef CAS; T. T. Nadasdi and D. W. Stephan, Inorg. Chem., 1993, 32, 5933 CrossRef CAS.
  7. T. T. Nadasdi and D. W. Stephan, Inorg. Chem., 1994, 33, 1532 CrossRef CAS.
  8. A. V. Firth and D. W. Stephan, Organometallics, 1997, 16, 2183 CrossRef CAS; Y. Huang, N. Etkin, R. R. Heyn, T. T. Nadasdi and D. W. Stephan, Organometallics, 1996, 15, 2320 CrossRef CAS; Y. Huang and D. W. Stephan, Organometallics, 1995, 14, 2835 CrossRef CAS.
  9. R. P. Burns and C. A. McAuliffe, Adv. Inorg. Radiochem., 1979, 22, 303 Search PubMed.
  10. (a) J. Locke and J. A. McCleverty, Inorg. Chem., 1996, 5, 1157; (b) J. A. McCleverty, T. A. James and E. J. Wharton, Inorg. Chem., 1969, 8, 1340 CrossRef CAS; (c) T. A. James and J. A. McCleverty, J. Chem. Soc. A, 1970, 3318 RSC.
  11. H. Köpf and T. Klapötke, J. Organomet. Chem., 1986, 307, 319 CrossRef.
  12. H. Köpf, K. Lange and J. Pickardt, J. Organomet. Chem., 1991, 420, 345 CrossRef; H. Balz, H. Köpf, K. Lange and J. Pickardt, Phosphorus Sulfur Silicon Relat. Elem., 1992, 65, 185 CAS.
  13. K. Tatsumi, J. Takeda, Y. Inoue, Y. Sekiguchi, M. Kohsaka and A. Nakamura, Angew. Chem., Int. Ed. Engl., 1985, 24, 332 CrossRef; K. Tatsumi, Y. Inoue and A. Nakamura, J. Organomet. Chem., 1993, 444, C25 CrossRef CAS.
  14. (a) A. J. Blake, J. A. Greig and M. Schröder, J. Chem. Soc., Dalton Trans., 1991, 529 Search PubMed; A. J. Blake, G. Reid and M. Schröder, J. Chem. Soc., Dalton Trans., 1992, 2987 RSC; A. J. Blake, R. M. Christie, Y. V. Roberts, M. J. Sullivan, M. Schröder and L. J. Yellowlees, J. Chem. Soc., Chem. Commun., 1992, 848 RSC.
  15. B. E. Bosch, M. Eisenhawer, B. Kersting, K. Kistschbaum, B. Krebs and D. M. Giolando, Inorg. Chem., 1996, 35, 6599 CrossRef CAS and refs. therein.
  16. H. Köpf and T. Klapötke, J. Organomet. Chem. Libr., 1988, 20, 343 Search PubMed; H. Köpf, Angew. Chem., Int. Ed. Engl., 1971, 10, 134 CrossRef; V. J. Amandrut, J. Sala-Pala, A. Fakhr, Y. Mugnier and C. Moise, J. Organomet. Chem., 1985, 292, 403 CrossRef CAS.
  17. G. H. Llinas, M. Mena, F. Palacios, P. Royo and R. Serrano, J. Organomet. Chem., 1988, 340, 37 CrossRef.
  18. M. J. Bunker, A. De Cian, M. L. H. Green, J. J. E. Moreau and N. Siganporia, J. Chem. Soc., Dalton Trans., 1980, 2155 RSC.
  19. R. D. Gorsich, J. Am. Chem. Soc., 1960, 82, 4211 CrossRef CAS.
  20. Siemens Analytical Instruments, Inc., Madison, WI, 1994; G. M. Sheldrick, SHELXTL PC, Siemens Analytical X-Ray Instruments, Inc., Madison, WI, 1994 Search PubMed.
Click here to see how this site uses Cookies. View our privacy policy here.